This Thesis considers peculiarities of nanoparticle formation from the gas in different systems. The main role of the surface condensation in the nanoparticle growth in metal flames was established through a series of experiments and was described by the developed model. The stagnation of the post-nucleation nanoparticle growth was experimentally revealed and theoretically explained. The influence of generation conditions on the post-processing nanoparticle properties was examined. The non-isothermal approach to correct the homogeneous nucleation theory was developed. The results of this work can be summarized in 3 categories: (1) Nanoparticle formation in metal flames. In this work, it was demonstrated that the surface condensation is a main process responsible for nanooxides growth during metal combustion. It was shown that the rate of this condensation growth is consistent with the exponential law, which could lead to the formation of the lognormal particle size distribution in the system, where the Brownian coagulation is suppressed. The post-nucleation stagnation of the nanoparticle growth was found. The particle overheating was suggested as a cause of the growth stagnation. The found stagnation leads to the accumulation of the supercritical clusters in the system generating nanoparticles. The role of these supercritical clusters in the nanoparticle agglomeration was considered. (2) Study of properties of nanoparticles generated in different metal flames. The light absorption, photoluminescence and magnetic properties of nanoparticles produced in different metal flames were examined. The significant broadening of the absorption edge was found in nanooxides produced by direct metal combustion. This broadening allowed one to excite the unforeseen photoluminescence from these nanoparticles. The significant light absorption in the visible light found in the titania particles produced by metal combustion allows one to consider these particles as a prospective photocatalyst. The unusual optical properties revealed were related to the extreme conditions of the nanoparticle formation, namely, to high energy release (about 5 eV per condensing molecule). The stabilization of spinel structure was found in iron oxide particles synthesized by iron combustion. It allowed one to produce nanoparticles with magnetization close to the high-limit value of the bulk. (3) Approach to correct the homogeneous nucleation theory. The existing homogeneous nucleation theory implies that nucleation occurs at isothermal conditions, i.e. subcritical clusters have the same temperature as the ambient gas does. However, the theory overestimates the actual nucleation rate and underestimates the critical cluster size. It is understandable that due to release of the latent heat of condensation, the cluster temperature in the nucleating system should be higher than the environment temperature. In this work, it was suggested the method to account for the cluster overheating during nucleation. It was demonstrated that the consistent description of the detailed balance in the nucleating system may allow one to evaluate magnitudes of overestimation of the actual nucleation rate and underestimation of the number of molecules in the critical cluster, usually obtained by the isothermal nucleation theory. The numerical estimates are in good agreement with the wellknown experimental results. The implications of the results to generation of atmospheric aerosols were discussed.

Abstract Cobalt-based complexes are widely used in industry and organic synthesis as catalysts for the oxidation of hydrocarbons. The Co/Mn/Br (known as "CAB system") catalyst system is effective for the oxidation of toluene. The Co/Mn/Br/Zr catalyst system is powerful for the oxidation of p-xylene, but not for the oxidation of toluene. [Co3O(OAc)5(OH)(py)3][PF6] (Co 3+ trimer 5) is more effective than [Co3O(OAc)6(py)3][PF6] (Co 3+ trimer 6) as a catalyst in the CAB catalyst system. Higher temperatures favour the oxidation of toluene. Zr 4+ does not enhance the oxidation of toluene. Zr 4+ could inhibit the oxidation of toluene in the combination of Co/Br/Zr, Co/Mn/Zr or Co/Zr. NHPI enhances the formation of benzyl alcohol, but the formation of other by-products is a problem for industrial processes. Complex(es) between cobalt, manganese and zirconium might be formed during the catalytic reaction. However, attempts at the preparation of complexes consisting of Co/Zr or Mn/Zr or Co3ZrP or Co8Zr4 clusters failed. The oxidation of cyclohexane to cyclohexanone and cyclohexanol is of great industrial significance. For the homogeneous catalysis at 50 o C and 3 bar N2 pressure, the activity order is: Mn(OAc)3 �2H2O > Mn12O12 cluster > Co 3+ trimer 6 > [Co3O(OAc)3(OH)2(py)5][PF6]2 (Co 3+ trimer 3) > Co 3+ trimer 5 > Co(OAc)2 �4H2O > [Co2(OAc)3(OH)2(py)4][PF6]-asym (Co dimerasym) > [Co2(OAc)3(OH)2(py)4][PF6]-sym (Co dimersym); whereas [Mn2CoO(OAc)6(py)3]�HOAc (Mn2Co complex) and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. But at 120 o C and 3 bar N2 pressure, the activity order is changed to: Co dimerasym > Co(OAc)2 �4H2O > Co trimer 3 and Mn(OAc)3 �2H2O > Co 3+ trimer 6 > Mn2Co complex > Co 3+ trimer 5 > Co dimersym > Mn12O12 cluster. The molar ratio of the products was close to cyclohexanol/cyclohexanone=2/1. Mn(II) acetate and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. Among those cobalt dimers and trimers, only the cobalt dimerasym survived after the stability tests, this means that [Co2(OAc)3(OH)2(py)4][PF6]-asym might be the active form for cobalt(II) acetate in the CAB system. Metal-substituted (silico)aluminophosphate-5 molecular sieves (MeAPO-5 and MeSAPO-5) are important heterogeneous catalysts for the oxidation of cyclohexane. The preparation of MeAPO-5 and MeSAPO-5 and their catalytic activities were studied. Pure MeAPO-5 and MeSAPO-5 are obtained and characterised. Four new pairs of bimetal-substituted MeAPO-5 and MeSAPO-5(CoZr, MnZr, CrZr and MnCo) were prepared successfully. Two novel trimetal-subtituted MeAPO-5 and MeSAPO-5 (MnCoZr) are reported here. Improved methods for the preparation of four monometal-substituted MeAPO-5 (Cr, Co, Mn and Zr) and for CoCe(S)APO-5 and CrCe(S)APO-5 are reported. Novel combinational mixing conditions for the formation of gel mixtures for Me(S)APO-5 syntheses have been developed. For the oxidation of cyclohexane by TBHP catalysed by MeAPO-5 and MeSAPO-5 materials, CrZrSAPO-5 is the only active MeSAPO-5 catalyst among those materials tested under conditions of refluxing in cyclohexane. Of the MeAPO-5 materials tested, whereas CrCeSAPO-5 has very little activity, CrZrAPO-5 and CrCeAPO-5 are very active catalysts under conditions of refluxing in cyclohexane. MnCoAPO-5, MnZrAPO-5 and CrAPO-5 are also active. When Cr is in the catalyst system, the product distribution is always cyclohexanone/cyclohexanol equals 2-3)/1, compared with 1/2 for other catalysts. For MeAPO-5, the activity at 150 o C and 10 bar N2 pressure is: CrZrAPO-5 > CrCeAPO-5 > CoZrAPO-5. For MeAPO-5 and MeSAPO-5, at 150 o C and 13 bar N2 pressure, the selectivity towards cyclohexanone is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5; and the selectivity towards cyclohexanol is: MnZrAPO-5 > CrZrAPO-5 > MnCoAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5. Overall the selectivity towards the oxidation of cyclohexane is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5. The amount of water in the system can affect the performance of CrCeAPO-5, but has almost no effect on CrZrAPO-5. Metal leaching is another concern in potential industrial applications of MeAPO-5 and MeSAPO-5 catalysts. The heterogeneous catalysts prepared in the present work showed very little metal leaching. This feature, coupled with the good selectivities and effectivities, makes them potentially very useful.

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The research in this thesis involves the synthesis and characterization of nanoparticle catalysts for oxidation reactions. It includes two projects: 1) polymer-stabilized Au, Pd and bimetallic AuPd nanoparticle catalysts for alcohol oxidation reactions, and 2) oxidative stabilities and catalytic activities of thiolate- and dithiolate-protected Au monolayer-protected clusters (MPCs).<p>n the first project, alcohol oxidations under mild conditions using polyvinylpyrrolidone (PVP)-stabilized Au, Pd and bimetallic AuPd nanoparticle catalysts in aqueous solutions have been investigated. The catalytic activities of the nanoparticles towards the oxidation of benzyl alcohol, 1-butanol, 2-butanol, 2-buten-1-ol and 1,4-butanediol indicate that bimetallic 1:3 Au:Pd nanoparticles have higher catalytic activities than Au, Pd and other bimetallic AuPd nanoparticles, and that selectivities towards specific products can often be tuned using bimetallic particles. In addition, advantages and disadvantages for the use of such nanoparticle catalysts as mild, environmentally-friendly oxidation catalysts have been examined. This work has recently been published in the Journal of Catalysis.<p>In the second project, 1-dodecanethiolate-, dithiolate-, and 1:1 mixed 1-dodecanethiolate/dithiolate-protected Au MPCs have been synthesized and their thermal stability, oxidative stability in the presence of oxygen and cyanide anions have been studied. These systematic investigations reveal the stability of Au MPCs can be tuned by choosing different thiolate ligands and oxidation conditions. Partially-oxidized thiolate-protected Au MPCs which have substrate-accessible surfaces and are stabilized by residual thiolate ligands show indications they will be promising catalysts. The catalytic activities of 1-dodecanethiolate-, dithiolate-, and 1:1 mixed 1-dodecanethiolate/dithiolate-protected Au MPCs for catalytic 4-nitrophenol reduction with sodium borohydride were investigated, and all the Au MPCs showed high catalytic activity for this reaction.

La catálisis es un campo de la ciencia que explora soluciones a los problemas ambientales como la contaminación, la eliminación de los residuos generados en el proceso de síntesis de materiales o la regeneración de los recursos naturales. En la presente Tesis, hemos reportado un estudio de cálculos DFT para la σ activación del enlace NH de amoníaco considerando las especies μ3-alquilidinos de titanio utilizando el complejo modelo [{Ti(η5-C5H5)(μ-O)}3(μ3-CH)]. Posteriormente, con el fin de analizar la hidroformilación asimétrica de estireno catalizada por complejos Rh-Binaphos, se han combinando estudios basados en la aproximación de la determinación del estado de transición y un análisis cualitativo a través de un descriptor molecular recién definido (volumen de distancia ponderada, VW). Usando nuestro conocimiento mecanicista anterior, hemos presentado un estudio QSPR para predecir la actividad y la enantioselectividad de la hidroformilación de estireno catalizada por complejos Rh-difosfinas. También, hemos desarrollado una nueva metodología 3D-QSSR para predecir la enantioselectividad basada en la cuantificación de la representación de diagramas por cuadrantes y aplicándola en el ciclopropanación asimétrica de alquenos catalizadas por complejos de cobre. / Catalysis is a field of science that explores solutions to environmental problems such as pollution, elimination of waste generated in the process of materials synthesis or regeneration of natural resources. In the present Thesis, we have reported a DFT study on the N-H σ-bond activation of ammonia by the µ3-alkylidyne titanium species using the [{Ti(η5-C5H5)(µ-O)}3(µ3-CH)] model complex. Afterwards, we have combined the TS-based approach and qualitative analysis through a newly defined molecular descriptor (distance-weighted volume, VW), in order to analyze the asymmetric hydroformylation of styrene catalyzed by Rh-binaphos complexes. Using our previous mechanistic knowledge, we have presented a QSPR study to predict the activity and the enantioselectivity in the hydroformylation of styrene catalyzed by Rh-diphosphane complexes. We have also developed a new methodology to predict enantioselectivity based on the quantitative quadrant-diagram representation of the catalysts and 3D-QSSR modeling; and we have applied it in the asymmetric cyclopropanation of alkenes catalyzed by copper complexes.

The research in this thesis involves the synthesis and characterization of nanoparticle catalysts for oxidation reactions. It includes two projects: 1) polymer-stabilized Au, Pd and bimetallic AuPd nanoparticle catalysts for alcohol oxidation reactions, and 2) oxidative stabilities and catalytic activities of thiolate- and dithiolate-protected Au monolayer-protected clusters (MPCs).<p>n the first project, alcohol oxidations under mild conditions using polyvinylpyrrolidone (PVP)-stabilized Au, Pd and bimetallic AuPd nanoparticle catalysts in aqueous solutions have been investigated. The catalytic activities of the nanoparticles towards the oxidation of benzyl alcohol, 1-butanol, 2-butanol, 2-buten-1-ol and 1,4-butanediol indicate that bimetallic 1:3 Au:Pd nanoparticles have higher catalytic activities than Au, Pd and other bimetallic AuPd nanoparticles, and that selectivities towards specific products can often be tuned using bimetallic particles. In addition, advantages and disadvantages for the use of such nanoparticle catalysts as mild, environmentally-friendly oxidation catalysts have been examined. This work has recently been published in the Journal of Catalysis.<p>In the second project, 1-dodecanethiolate-, dithiolate-, and 1:1 mixed 1-dodecanethiolate/dithiolate-protected Au MPCs have been synthesized and their thermal stability, oxidative stability in the presence of oxygen and cyanide anions have been studied. These systematic investigations reveal the stability of Au MPCs can be tuned by choosing different thiolate ligands and oxidation conditions. Partially-oxidized thiolate-protected Au MPCs which have substrate-accessible surfaces and are stabilized by residual thiolate ligands show indications they will be promising catalysts. The catalytic activities of 1-dodecanethiolate-, dithiolate-, and 1:1 mixed 1-dodecanethiolate/dithiolate-protected Au MPCs for catalytic 4-nitrophenol reduction with sodium borohydride were investigated, and all the Au MPCs showed high catalytic activity for this reaction.

Abstract Cobalt-based complexes are widely used in industry and organic synthesis as catalysts for the oxidation of hydrocarbons. The Co/Mn/Br (known as "CAB system") catalyst system is effective for the oxidation of toluene. The Co/Mn/Br/Zr catalyst system is powerful for the oxidation of p-xylene, but not for the oxidation of toluene. [Co3O(OAc)5(OH)(py)3][PF6] (Co 3+ trimer 5) is more effective than [Co3O(OAc)6(py)3][PF6] (Co 3+ trimer 6) as a catalyst in the CAB catalyst system. Higher temperatures favour the oxidation of toluene. Zr 4+ does not enhance the oxidation of toluene. Zr 4+ could inhibit the oxidation of toluene in the combination of Co/Br/Zr, Co/Mn/Zr or Co/Zr. NHPI enhances the formation of benzyl alcohol, but the formation of other by-products is a problem for industrial processes. Complex(es) between cobalt, manganese and zirconium might be formed during the catalytic reaction. However, attempts at the preparation of complexes consisting of Co/Zr or Mn/Zr or Co3ZrP or Co8Zr4 clusters failed. The oxidation of cyclohexane to cyclohexanone and cyclohexanol is of great industrial significance. For the homogeneous catalysis at 50 o C and 3 bar N2 pressure, the activity order is: Mn(OAc)3 �2H2O > Mn12O12 cluster > Co 3+ trimer 6 > [Co3O(OAc)3(OH)2(py)5][PF6]2 (Co 3+ trimer 3) > Co 3+ trimer 5 > Co(OAc)2 �4H2O > [Co2(OAc)3(OH)2(py)4][PF6]-asym (Co dimerasym) > [Co2(OAc)3(OH)2(py)4][PF6]-sym (Co dimersym); whereas [Mn2CoO(OAc)6(py)3]�HOAc (Mn2Co complex) and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. But at 120 o C and 3 bar N2 pressure, the activity order is changed to: Co dimerasym > Co(OAc)2 �4H2O > Co trimer 3 and Mn(OAc)3 �2H2O > Co 3+ trimer 6 > Mn2Co complex > Co 3+ trimer 5 > Co dimersym > Mn12O12 cluster. The molar ratio of the products was close to cyclohexanol/cyclohexanone=2/1. Mn(II) acetate and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. Among those cobalt dimers and trimers, only the cobalt dimerasym survived after the stability tests, this means that [Co2(OAc)3(OH)2(py)4][PF6]-asym might be the active form for cobalt(II) acetate in the CAB system. Metal-substituted (silico)aluminophosphate-5 molecular sieves (MeAPO-5 and MeSAPO-5) are important heterogeneous catalysts for the oxidation of cyclohexane. The preparation of MeAPO-5 and MeSAPO-5 and their catalytic activities were studied. Pure MeAPO-5 and MeSAPO-5 are obtained and characterised. Four new pairs of bimetal-substituted MeAPO-5 and MeSAPO-5(CoZr, MnZr, CrZr and MnCo) were prepared successfully. Two novel trimetal-subtituted MeAPO-5 and MeSAPO-5 (MnCoZr) are reported here. Improved methods for the preparation of four monometal-substituted MeAPO-5 (Cr, Co, Mn and Zr) and for CoCe(S)APO-5 and CrCe(S)APO-5 are reported. Novel combinational mixing conditions for the formation of gel mixtures for Me(S)APO-5 syntheses have been developed. For the oxidation of cyclohexane by TBHP catalysed by MeAPO-5 and MeSAPO-5 materials, CrZrSAPO-5 is the only active MeSAPO-5 catalyst among those materials tested under conditions of refluxing in cyclohexane. Of the MeAPO-5 materials tested, whereas CrCeSAPO-5 has very little activity, CrZrAPO-5 and CrCeAPO-5 are very active catalysts under conditions of refluxing in cyclohexane. MnCoAPO-5, MnZrAPO-5 and CrAPO-5 are also active. When Cr is in the catalyst system, the product distribution is always cyclohexanone/cyclohexanol equals 2-3)/1, compared with 1/2 for other catalysts. For MeAPO-5, the activity at 150 o C and 10 bar N2 pressure is: CrZrAPO-5 > CrCeAPO-5 > CoZrAPO-5. For MeAPO-5 and MeSAPO-5, at 150 o C and 13 bar N2 pressure, the selectivity towards cyclohexanone is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5; and the selectivity towards cyclohexanol is: MnZrAPO-5 > CrZrAPO-5 > MnCoAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5. Overall the selectivity towards the oxidation of cyclohexane is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5. The amount of water in the system can affect the performance of CrCeAPO-5, but has almost no effect on CrZrAPO-5. Metal leaching is another concern in potential industrial applications of MeAPO-5 and MeSAPO-5 catalysts. The heterogeneous catalysts prepared in the present work showed very little metal leaching. This feature, coupled with the good selectivities and effectivities, makes them potentially very useful.

Thesis (doctoral)--Rheinische Friedrich-Wilhelms-Universität Bonn, 2005. / Includes vita. Includes bibliographical references (p. 90-93).

Macroscopic ductility is promoted in bulk metallic glasses by both composite reinforcements (at low temperatures) and by the activation of viscous flow mechanisms (at high temperatures). It is of fundamental interest to understand deformation physics when both of these strategies are employed at the same time. Despite the quickly growing literature around the room-temperature mechanical properties of metallic glass matrix composites (MGMCs), the deformation behavior of MGMCs over a wide range of temperatures and strain rates has yet to be systematically investigated, especially at high temperatures close to Tg. Here the high temperature compressive behavior of Zr-based MGMCs with in-situ reinforcements is explored systematically over a series of strain rates. Additionally, the volume fraction of second-phase reinforcements was tailored to explore its effect on both inhomogeneous and homogeneous deformation modes. / Singapore-MIT Alliance (SMA)